COMPUTATIONAL INSIGHTS INTO THE ESTERIFICATION OF LAURIC ACID (C12) WITH α-BISABOLOL OVER CeO2 AS A HETEROGENEOUS CATALYST

Autores/as

DOI:

https://doi.org/10.61164/jzjcha21

Palabras clave:

Esterification, Heterogeneous catalysis, Lauric acid (C12), α-bisabolol alcohol, Computational chemistry

Resumen

In this work, we conducted a theoretical investigation of the esterification of lauric acid (C12) with the natural unsaturated alcohol (-)-α-bisabolol, considering both uncatalyzed and CeO2-catalyzed pathways. Molecular structures were optimized using a combination of semi-empirical methods and Density Functional Theory (DFT), enabling the calculation of key parameters such as dipole moments, electrostatic potential maps, infrared spectra, and frontier molecular orbitals (HOMO and LUMO). For the uncatalyzed reactions, we evaluated thermodynamic descriptors, including enthalpy (∆H⁰), Gibbs free energy (∆G⁰), and entropy (∆S⁰), to gain mechanistic insights. Reaction pathways were further explored through a hybrid QM/MM strategy combined with Molecular Dynamics (MD) simulations. The esterification of lauric acid with (-)-α-bisabolol proceeds via an SN2-type mechanism. The findings indicate that, in the absence of a catalyst, the reaction is not spontaneous; however, the use of CeO2 as a heterogeneous catalyst significantly enhances the spontaneity, favoring the formation of (-)-α-bisabolol laurate.

Descargas

Los datos de descarga aún no están disponibles.

Biografía del autor/a

  • Wellington da Conceição Lobato do Nascimento, Federal University of Maranhão - UFMA

    PhD student in Chemistry 

  • Alberto Monteiro dos Santos, Brandeis University

    Departament of Chemistry 

  • Natanael de Sousa Sousa, Federal University of Maranhão – UFMA

    PhD in Chemistry 

  • Carlos Alberto Lira Júnior, Federal University of Maranhão – UFMA

    PhD in Biotechnology 

  • Jerônimo Lameira Silva, Federal University of Pará – UFPA

    Institute of Biological Sciences 

  • Adeilton Pereira Maciel, Federal University of Rio Grande of Norte – UFRN

    Department of Chemistry 

Referencias

[1] Bhatia SK, Bhatia RK, Jeon J, Pugazhendhi A, Awasthi MK, Kumar D, Kumar G, Yoon J, Yang Y (2021) An overview on advancements in biobased transesterification methods for biodiesel production: Oil resources, extraction, biocatalysts, and process intensification technologies, Fuel. 285:119117. https://doi.org/10.1016/j.fuel.2020.119117. DOI: https://doi.org/10.1016/j.fuel.2020.119117

[2] Derr KM, Lopez CV, Maladeniya CP, Tennyson AG, Smith RC (2023) Transesterification-vulcanization route to durable composites from post-consumer poly (ethylene terephthalate), terpenoids, and industrial waste sulfur, J. Polym. Sci. 61:3075-3086. https://doi.org/10.1002/pol.20230503. DOI: https://doi.org/10.1002/pol.20230503

[3] Baskar G, Aiswarya R (2016) Trends in catalytic production of biodiesel from various feedstocks. Renew. and Sustain. Energy Rev. 57:496-504. https://doi.org/10.1016/j.rser.2015.12.101. DOI: https://doi.org/10.1016/j.rser.2015.12.101

[4] Suppes GJ, Bockwinkel K, Lucas S, Botts JB, Mason MH, Heppert JA (2001) Calcium Carbonate Catalyzed of Fat and Oils, J Am Oil Chem Soc. 78:139-146. https://doi.org/10.1007/s11746-001-0234-y. DOI: https://doi.org/10.1007/s11746-001-0234-y

[5] Appaturi JN, Andas J, Ma YK, Phoon BL, Batagarawa SM, Khoerunnisa F, Hussin MZ, Ng EP (2022) Recent advances in heterogeneous catalysts for the synthesis of alkyl levulinate biofuel additives from renewable levulinic acid: A comprehensive review, Fuel 323:124362. https://doi.org/10.1016/j.fuel.2022.124362. DOI: https://doi.org/10.1016/j.fuel.2022.124362

[6] Trovarelli A., Catalysis by ceria and Related Materials. 2. ed. Imperial College Press, London. 2002. https://doi.org/10.1142/p249. DOI: https://doi.org/10.1142/p249

[7] Elgharbawy AS, Sadik WA, Sadek OM, Kasaby MA (2021) A review on biodiesel feedstocks and production technologies, J. Chil. Chem. Soc. 66:5098–5106. https://dx.doi.org/10.4067/S0717-97072021000105098. DOI: https://doi.org/10.4067/S0717-97072021000105098

[8] Matsue M, Mori Y, Nagase S, Sugiyama Y, Hirano R, Ogai K, Ogura K, Kurihara S, Okamoto S. (2019) Measuring the Antimicrobial Activity of Lauric Acid against Various Bacteria in Human Gut Microbiota Using a New Method, Cell Transplant. 28:1258–1268. https://dx.doi.org/10.1177/0963689719881366. DOI: https://doi.org/10.1177/0963689719881366

[9] Alexandre JYNH, Cavalcante FTT, Freitas LM, Castro AP, Borges PT, Sousa Junior PG, Filho MNR, Lopes ASS, Fonseca AM, Lomonaco D, Rios MAS, Santos JCS (2022) A Theoretical and Experimental Study for Enzymatic Biodiesel Production from Babassu Oil (Orbignya sp.) Using Eversa Lipase, Catalysts 12:1322. https://doi.org/10.3390/catal12111322. DOI: https://doi.org/10.3390/catal12111322

[10] Rangel NVP, Silva LP, Pinheiro VS, Figueredo IM, Campos OS, Costa SN, Luna FMT, Cavalcante Jr. CL, Marinho ES, Lima-Neto P, Maria Rios MA (2021) Effect of additives on the oxidative stability and corrosivity of biodiesel samples derived from babassu oil and residual frying oil: An experimental and theoretical assessment, Fuel. 291:119939. https://doi.org/10.1016/j.fuel.2020.119939. DOI: https://doi.org/10.1016/j.fuel.2020.119939

[11] Maciel AP (2016) Babassu biofuels: technical essay on opportunities for producing biofuels from babassu coconut. EDUFMA, São Luís-MA, Brazil.

[12] Souza ERL, Gomes NML, J. H. A. (2021) Propriedades farmacológicas do Sesquiterpeno α-Bisabolol: uma breve revisão. Arch Health Invest., 10:1–6. https://doi.org/10.21270/archi.v10i1.3183. DOI: https://doi.org/10.21270/archi.v10i1.3183

[13] Tan H, Lou B, Shen A & Ning C. (2023) Experimental and theoretical research on one-step oxidative esterification of methyl acrolein with methanol. Ind. Eng. Chem. Res., 62:21609-21618. https://doi.org/10.1021/acs.iecr.3c03136. DOI: https://doi.org/10.1021/acs.iecr.3c03136

[14] Majidian S, Rashid HI, Naghdi Y, Irani M, & Samadi S. (2025) Copper‐Catalyzed Simultaneous Dehydrogenation and Enantioselective Allylic Oxidation of Alkanes Using Chiral Heterogeneous Ligands to Produce Allylic Esters and Theoretical Investigation of the Mechanism. Appl. Organomet. Chem., 39:e7857. https://doi.org/10.1002/aoc.7857. DOI: https://doi.org/10.1002/aoc.7857

[15] Stewart JJP (2009) Application of the PM6 method to modeling the solid state, J. Mol. Model., 15:765–805. https://doi.org/10.1007/s00894-008-0299-7. DOI: https://doi.org/10.1007/s00894-008-0420-y

[16] Praveen PA, Saravanapriya D, Bhat SV, Arulkannan K, Kanagasekaran T (2024) Comprehensive analysis of DFT-3C methods with B3LYP and experimental data to model optoelectronic properties of tetracene, Mat. Sci. Semicond. Process., 158:108159. https://doi.org/10.1016/j.mssp.2024.108159. DOI: https://doi.org/10.1016/j.mssp.2024.108159

[17] Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals, Theor. Chem. Account. 120:215–241. https://doi.org/10.1007/s00214-007-0310-x. DOI: https://doi.org/10.1007/s00214-007-0310-x

[18] Field MJ (2008) The pDynamo Program for Molecular Simulations using Hybrid Quantum Chemical and Molecular Mechanical Potentials, J. Chem. Theory Comput., 4:1151–1161. https://doi.org/10.1021/ct800092p. DOI: https://doi.org/10.1021/ct800092p

[19] Neese F, Wennmohs F, Becker U, Riplinger C (2020) The ORCA quantum chemistry program package, J. Chem. Phys., 152:224108. https://doi.org/10.1063/5.0004608. DOI: https://doi.org/10.1063/5.0004608

[20] Zhu X, Lopes PEM, MacKerell Jr AD (2013) Recent developments and applications of the CHARMM force fields, WIREs Comput Mol Sci., 3:386–408. https://doi.org/10.1002/wcms.74. DOI: https://doi.org/10.1002/wcms.74

[21] Reed AE, Weinhold F (1985) Natural Population Analysis. J Chem Phys., 83:735–746. https://doi.org/10.1063/1.449486. DOI: https://doi.org/10.1063/1.449486

[22] Politzer P, Murray J (2002) The fundamental nature and role of the electrostatic potential in atoms and molecules, Theor Chem Acc., 108:134–142. https://doi.org/10.1007/s00214-002-0363-9. DOI: https://doi.org/10.1007/s00214-002-0363-9

[23] Fleming (1976) Frontier Orbitals and Organic Chemical Reactions. John Wiley & Sons, New York.

[24] Sinclair RG, McKay AF, Jones RN (1952) The infrared absorption spectra of saturated fatty acids and esters, J. Am. Chem. Soc., 74:6070–6075. https://doi.org/10.1021/ja01130a033. DOI: https://doi.org/10.1021/ja01130a033

[25] Oliveira FS, Freitas TS, Cruz RP, Costa MS, Pereira RLS, Quintans-Júnior LJ, Andrade TA, Menezes PP, Sousa BMH, Nunes PS, Serafini MR, Menezes IRA, Araújo AAS, Coutinho HDM (2017) Evaluation of the antibacterial and modulatory potential of a-bisabolol, b-cyclodextrin and a-bisabolol/b-cyclodextrin complex, Biomed Pharmacother 93:87–94. https://doi.org/10.1016/j.biopha.2017.06.020. DOI: https://doi.org/10.1016/j.biopha.2017.06.020

[26] Mucelini J, Costa-Amaral R, Seminovski Y, Silva JLF (2018) Ab initio investigation of the formation of ZrO2-like structures upon the adsorption of Zrn on the CeO2 (111) surface, J. Chem. Phys., 149:164701. https://doi.org/10.1063/1.5063732. DOI: https://doi.org/10.1063/1.5063732

Descargas

Publicado

2025-11-19

Número

Vol. 20 Núm. 2 (2025): REMUNOM - ISSN 2178-6925

Sección

Artigos

Licencia

Derechos de autor 2025 Wellington da Conceicao Lobato do Nascimento, Alberto Monteiro dos Santos, Natanael de Sousa Sousa, Carlos Alberto Lira Júnior, Jerônimo Lameira Silva, Adeilton Pereira Maciel

Creative Commons License

Esta obra está bajo una licencia internacional Creative Commons Atribución 4.0.

Autores que publicam nesta revista concordam com os seguintes termos:
 

  • Autores mantém os direitos autorais e concedem à revista o direito de primeira publicação, com o trabalho simultaneamente licenciado sob a Licença Creative Commons Attribution que permite o compartilhamento do trabalho com reconhecimento da autoria e publicação inicial nesta revista;
  • Autores têm autorização para assumir contratos adicionais separadamente, para distribuição não-exclusiva da versão do trabalho publicada nesta revista (ex.: publicar em repositório institucional ou como capítulo de livro), com reconhecimento de autoria e publicação inicial nesta revista, desde que adpatado ao template do repositório em questão;
  • Autores têm permissão e são estimulados a publicar e distribuir seu trabalho online (ex.: em repositórios institucionais ou na sua página pessoal) a qualquer ponto antes ou durante o processo editorial, já que isso pode gerar alterações produtivas, bem como aumentar o impacto e a citação do trabalho publicado (Veja O Efeito do Acesso Livre).
  • Os autores são responsáveis por inserir corretamente seus dados, incluindo nome, palavras-chave, resumos e demais informações, definindo assim a forma como desejam ser citados. Dessa forma, o corpo editorial da revista não se responsabiliza por eventuais erros ou inconsistências nesses registros.

 

POLÍTICA DE PRIVACIDADE

Os nomes e endereços informados nesta revista serão usados exclusivamente para os serviços prestados por esta publicação, não sendo disponibilizados para outras finalidades ou a terceiros.

Obs: todo o conteúdo do trabalho é de responsabilidade do autor e orientador.

Cómo citar

COMPUTATIONAL INSIGHTS INTO THE ESTERIFICATION OF LAURIC ACID (C12) WITH α-BISABOLOL OVER CeO2 AS A HETEROGENEOUS CATALYST. (2025). Revista Multidisciplinar Do Nordeste Mineiro, 20(2), 1-21. https://doi.org/10.61164/jzjcha21